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Reversible pH-responsive supramolecular aggregates from viologen based amphiphiles – A molecular design perspective

Soft Matter, 2024, Accepted Manuscript
DOI: 10.1039/D4SM00695J, Paper
Redhills L. Narendran, Archita Patnaik
pH responsive self-assembled supramolecular systems in water hold tremendous promise spanning across the various realms of science and technology. Herein, we report the design and synthesis of benzyl viologen (BV)...
The content of this RSS Feed (c) The Royal Society of Chemistry




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A generalized model for predicting different morphologies of bacterial swarming on a porous solid surface

Soft Matter, 2024, Accepted Manuscript
DOI: 10.1039/D4SM01072H, Paper
Uttam Kumar, Pushpavanam Subramaniam
In this study, we develop a comprehensive two-phase model to analyze the dynamics of bacterial swarming on porous substrates. The two distinct phases under consideration are the cell and aqueous...
The content of this RSS Feed (c) The Royal Society of Chemistry




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Iconography of Security

Molly Wilson and Eileen Wagner battle the age old Christmas issues of right and wrong, good and evil, and how the messages we send through iconography design can impact the decisions users make around important issues of security. Are you icons wise men, or are they actually King Herod?


Congratulations, you’re locked out! The paradox of security visuals

Designers of technology are fortunate to have an established visual language at our fingertips. We try to use colors and symbols in a way that is consistent with people’s existing expectations. When a non-designer asks a designer to “make it intuitive,” what they’re really asking is, “please use elements people already know, even if the concept is new.”

Lots of options for security icons

We’re starting to see more consistency in the symbols that tech uses for privacy and security features, many of them built into robust, standardized icon sets and UI kits. To name a few: we collaborated with Adobe in 2018 to create the Vault UI Kit, which includes UI elements for security, like touch ID login and sending a secure copy of a file. Adobe has also released a UI kit for cookie banners.

Activity log from the Vault Secure UI Kit, by Adobe and Simply Secure.
Cookie banner, from the Cookie Banner UI Kit, by Adobe.

Even UI kits that aren’t specialized in security and privacy include icons that can be used to communicate security concepts, like InVision’s Smart Home UI Kit. And, of course, nearly every icon set has security-related symbols, from Material Design to Iconic.

Key, lock, unlock, shield, and warning icons from Iconic.
A selection of security-related icons from Material Design.
Security shields from a selection of Chinese apps, 2014. From a longer essay by Dan Grover.

Many of these icons allude to physical analogies for the states and actions we’re trying to communicate. Locks and keys; shields for protection; warning signs and stop signs; happy faces and sad faces. Using these analogies helps build a bridge from the familiar, concrete world of door locks and keyrings to the unfamiliar, abstract realm of public- and private-key encryption.

flickr/Jim Pennucci
GPG Keychain, an open-source application for managing encryption keys. Image: tutsplus.com

When concepts don’t match up

Many of the concepts we’re working with are pairs of opposites. Locked or unlocked. Private or public. Trusted or untrusted. Blocked or allowed. Encouraged or discouraged. Good or evil. When those concept pairs appear simultaneously, however, we quickly run into UX problems.

Take the following example. Security is good, right? When something is locked, that means you’re being responsible and careful, and nobody else can access it. It’s protected. That’s cause for celebration. Being locked and protected is a good state.

“Congratulations, you’re locked out!”

Whoops.

If the user didn’t mean to lock something, or if the locked state is going to cause them any inconvenience, then extra security is definitely not good news.

Another case in point: Trust is good, right? Something trusted is welcome in people’s lives. It’s allowed to enter, not blocked, and it’s there because people wanted it there. So trusting and allowing something is good.

“Good job, you’ve downloaded malware!”

Nope. Doesn’t work at all. What if we try the opposite colors and iconography?

That’s even worse. Even though we, the designers, were trying both times to keep the user from downloading malware, the user’s actual behavior makes our design completely nonsensical.

Researchers from Google and UC Berkeley identified this problem in a 2016 USENIX paper analyzing connection security indicators. They pointed out that, when somebody clicks through a warning to an “insecure” website, the browser will show a “neutral or positive indicator” in the URL bar – leading them to think that the website is now safe. Unlike our example above, this may not look like nonsense from the user point of view, but from a security standpoint, suddenly showing “safe/good” without any actual change in safety is a pretty dangerous move.

The deeper issue

Now, one could file these phenomena under “mismatching iconography,” but we think there is a deeper issue here that concerns security UI in particular. Security interface design pretty much always has at least a whiff of “right vs. wrong.” How did this moralizing creep into an ostensibly technical realm?

Well, we usually have a pretty good idea what we’d like people to do with regards to security. Generally speaking, we’d like them to be more cautious than they are (at least, so long as we’re not trying to sneak around behind their backs with confusing consent forms and extracurricular data use). Our well-intentioned educational enthusiasm leads us to use little design nudges that foster better security practices, and that makes us reach into the realm of social and psychological signals. But these nudges can easily backfire and turn into total nonsense.

Another example: NoScript

“No UX designer would be dense enough to make these mistakes,” you might be thinking.

Well, we recently did a redesign of the open-source content-blocking browser extension NoScript, and we can tell you from experience: finding the right visual language for pairs of opposites was a struggle.

NoScript is a browser extension that helps you block potential malware from the websites you’re visiting. It needs to communicate a lot of states and actions to users. A single script can be blocked or allowed. A source of scripts can be trusted or untrusted. NoScript is a tool for the truly paranoid, so in general, wants to encourage blocking and not trusting. But:

“An icon with a crossed-out item is usually BAD, and a sign without anything is usually GOOD. But of course, here blocking something is actually GOOD, while blocking nothing is actually BAD. So whichever indicators NoScript chooses, they should either aim to indicate system state [allow/block] or recommendation [good/bad], but not both. And in any case, NoScript should probably stay away from standard colors and icons.”

So we ended up using hardly any of the many common security icons available. No shields, no alert! signs, no locked locks, no unlocked locks. And we completely avoided the red/green palette to keep from taking on unintended meaning.

Navigating the paradox

Security recommendations appear in most digital services are built nowadays. As we move into 2020, we expect to see a lot more conscious choice around colors, icons, and words related to security. For a start, Firefox already made a step in the right direction by streamlining indicators for SSL encryption as well as content blocking. (Spoilers: they avoided adding multiple dimensions of indicators, too!)

The most important thing to keep in mind, as you’re choosing language around security and privacy features, is: don’t conflate social and technical concepts. Trusting your partner is good. Trusting a website? Well, could be good, could be bad. Locking your bike? Good idea. Locking a file? That depends.

Think about the technical facts you’re trying to communicate. Then, and only then, consider if there’s also a behavioral nudge you want to send, and if you are, try to poke holes in your reasoning. Is there ever a case where your nudge could be dangerous? Colors, icons, and words give you a lot of control over how exactly people experience security and privacy features. Using them in a clear and consistent way will help people understand their choices and make more conscious decisions around security.


About the author

Molly Wilson is a designer by training and a teacher at heart: her passion is leveraging human-centered design to help make technology clear and understandable. She has been designing and leading programs in design thinking and innovation processes since 2010, first at the Stanford d.school in Palo Alto, CA and later at the Hasso-Plattner-Institut School of Design Thinking in Potsdam, Germany. Her work as an interaction designer has focused on complex products in finance, health, and education. Outside of work, talk to her about cross-cultural communication, feminism, DIY projects, and visual note-taking.

Molly holds a master’s degree in Learning, Design, and Technology from Stanford University, and a bachelor’s degree magna cum laude in History of Science from Harvard University. See more about her work and projects at http://molly.is.

Eileen Wagner is Simply Secure’s in-house logician. She advises teams and organizations on UX design, supports research and user testing, and produces open resources for the community. Her focus is on information architecture, content strategy, and interaction design. Sometimes she puts on her admin hat and makes sure her team has the required infrastructure to excel.

She previously campaigned for open data and civic tech at the Open Knowledge Foundation Germany. There she helped establish the first public funding program for open source projects in Germany, the Prototype Fund. Her background is in analytic philosophy (BA Cambridge) and mathematical logic (MSc Amsterdam), and she won’t stop talking about barbershop music.

More articles by Molly Wilson & Eileen




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Building a Dictaphone Using Media Recorder and getUserMedia

Chris Mills brushes up his shorthand and shows how the MediaStream Recording API in modern browsers can be used to capture audio directly from the user’s device. Inching ever closer to the capabilities of native software, it truly is an exciting time to be a web developer.


The MediaStream Recording API makes it easy to record audio and/or video streams. When used with MediaDevices.getUserMedia(), it provides an easy way to record media from the user’s input devices and instantly use the result in web apps. This article shows how to use these technologies to create a fun dictaphone app.

A sample application: Web Dictaphone

To demonstrate basic usage of the MediaRecorder API, we have built a web-based dictaphone. It allows you to record snippets of audio and then play them back. It even gives you a visualisation of your device’s sound input, using the Web Audio API. We’ll just concentrate on the recording and playback functionality in this article, for brevity’s sake.

You can see this demo running live, or grab the source code on GitHub. This has pretty good support on modern desktop browsers, but pretty patchy support on mobile browsers currently.

Basic app setup

To grab the media stream we want to capture, we use getUserMedia(). We then use the MediaRecorder API to record the stream, and output each recorded snippet into the source of a generated <audio> element so it can be played back.

We’ll first declare some variables for the record and stop buttons, and the <article> that will contain the generated audio players:

const record = document.querySelector('.record');
const stop = document.querySelector('.stop');
const soundClips = document.querySelector('.sound-clips');

Next, we set up the basic getUserMedia structure:

if (navigator.mediaDevices && navigator.mediaDevices.getUserMedia) {
   console.log('getUserMedia supported.');
   navigator.mediaDevices.getUserMedia (
      // constraints - only audio needed for this app
      {
         audio: true
      })

      // Success callback
      .then(function(stream) {

      })

      // Error callback
      .catch(function(err) {
         console.log('The following `getUserMedia` error occured: ' + err);
      }
   );
} else {
   console.log('getUserMedia not supported on your browser!');
}

The whole thing is wrapped in a test that checks whether getUserMedia is supported before running anything else. Next, we call getUserMedia() and inside it define:

  • The constraints: Only audio is to be captured for our dictaphone.
  • The success callback: This code is run once the getUserMedia call has been completed successfully.
  • The error/failure callback: The code is run if the getUserMedia call fails for whatever reason.

Note: All of the code below is found inside the getUserMedia success callback in the finished version.

Capturing the media stream

Once getUserMedia has created a media stream successfully, you create a new Media Recorder instance with the MediaRecorder() constructor and pass it the stream directly. This is your entry point into using the MediaRecorder API — the stream is now ready to be captured into a <Blob>, in the default encoding format of your browser.

const mediaRecorder = new MediaRecorder(stream);

There are a series of methods available in the MediaRecorder interface that allow you to control recording of the media stream; in Web Dictaphone we just make use of two, and listen to some events. First of all, MediaRecorder.start() is used to start recording the stream once the record button is pressed:

record.onclick = function() {
  mediaRecorder.start();
  console.log(mediaRecorder.state);
  console.log("recorder started");
  record.style.background = "red";
  record.style.color = "black";
}

When the MediaRecorder is recording, the MediaRecorder.state property will return a value of “recording”.

As recording progresses, we need to collect the audio data. We register an event handler to do this using mediaRecorder.ondataavailable:

let chunks = [];

mediaRecorder.ondataavailable = function(e) {
  chunks.push(e.data);
}

Last, we use the MediaRecorder.stop() method to stop the recording when the stop button is pressed, and finalize the Blob ready for use somewhere else in our application.

stop.onclick = function() {
  mediaRecorder.stop();
  console.log(mediaRecorder.state);
  console.log("recorder stopped");
  record.style.background = "";
  record.style.color = "";
}

Note that the recording may also stop naturally if the media stream ends (e.g. if you were grabbing a song track and the track ended, or the user stopped sharing their microphone).

Grabbing and using the blob

When recording has stopped, the state property returns a value of “inactive”, and a stop event is fired. We register an event handler for this using mediaRecorder.onstop, and construct our blob there from all the chunks we have received:

mediaRecorder.onstop = function(e) {
  console.log("recorder stopped");

  const clipName = prompt('Enter a name for your sound clip');

  const clipContainer = document.createElement('article');
  const clipLabel = document.createElement('p');
  const audio = document.createElement('audio');
  const deleteButton = document.createElement('button');

  clipContainer.classList.add('clip');
  audio.setAttribute('controls', '');
  deleteButton.innerHTML = "Delete";
  clipLabel.innerHTML = clipName;

  clipContainer.appendChild(audio);
  clipContainer.appendChild(clipLabel);
  clipContainer.appendChild(deleteButton);
  soundClips.appendChild(clipContainer);

  const blob = new Blob(chunks, { 'type' : 'audio/ogg; codecs=opus' });
  chunks = [];
  const audioURL = window.URL.createObjectURL(blob);
  audio.src = audioURL;

  deleteButton.onclick = function(e) {
    let evtTgt = e.target;
    evtTgt.parentNode.parentNode.removeChild(evtTgt.parentNode);
  }
}

Let’s go through the above code and look at what’s happening.

First, we display a prompt asking the user to name their clip.

Next, we create an HTML structure like the following, inserting it into our clip container, which is an <article> element.

<article class="clip">
  <audio controls></audio>
  <p>_your clip name_</p>
  <button>Delete</button>
</article>

After that, we create a combined Blob out of the recorded audio chunks, and create an object URL pointing to it, using window.URL.createObjectURL(blob). We then set the value of the <audio> element’s src attribute to the object URL, so that when the play button is pressed on the audio player, it will play the Blob.

Finally, we set an onclick handler on the delete button to be a function that deletes the whole clip HTML structure.

So that’s basically it — we have a rough and ready dictaphone. Have fun recording those Christmas jingles! As a reminder, you can find the source code, and see it running live, on the MDN GitHub.


This article is based on Using the MediaStream Recording API by Mozilla Contributors, and is licensed under CC-BY-SA 2.5.


About the author

Chris Mills manages the MDN web docs writers’ team at Mozilla, which involves spreadsheets, meetings, writing docs and demos about open web technologies, and occasional tech talks at conferences and universities. He used to work for Opera and W3C, and enjoys playing heavy metal drums and drinking good beer.

More articles by Chris




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A Modern Typographic Scale

Rob Weychert reaches for the top notes to sing us a song of typographic scale. A little attention to scale and to the mathematics will help you to hit a high note with your designs this Christmas and beyond.


I’ve been studying music theory this year. While some of its core concepts were already familiar to me, much of their specifics were not. Or so I thought. A funny thing happened when I was learning the major scales.

While playing through a song I had written some years before, I started picking it apart to see how it correlated with the theory I was learning. I had composed the melody without any thought to what the specific notes were, but as I started to transcribe them, a pattern quickly emerged: all the B’s and E’s were flat and the rest of the notes were natural. Lo and behold, long before my music theory studies began, I had written a song in B♭ major. My ears already knew how the major scales worked even if my brain didn’t. (If you know how “do re mi fa so la ti do” is supposed to sound tonally, then your ears know, too.)

When music is composed to a scale, it sounds “right” to us. And just as our ears appreciate harmony and melody with a rational basis, our eyes can appreciate the same concepts applied to spatial relationships.

Have you ever struggled with sizing type in a design project, especially when you need more than just one or two sizes? Have you ever despaired at the number of ad-hoc type sizes on your site spiraling out of control over time? It could be that you’ve been composing the typographic equivalent of a cacophonous symphony. And the first thing any composer will tell you to do is to get that thing on a scale.

Meet the typographic scale

You don’t need to know music theory to work with a typographic scale. You only need to know that a scale is a range of values with an established mathematic relationship. For a typographic scale, that relationship is frequently a steady interval between type sizes. Depending on what you need your type to do, the interval might be fixed (e.g. each size is two pixels bigger than the size before it) or it might be proportional (e.g. each size is twice as big as the size before it). I personally rarely find fixed intervals useful, so I’ll be focusing on proportional intervals.

The most important thing to understand about proportional intervals is thankfully not complicated: The bigger the intervals are, the more drastic the size differences will be in your scale. If your layout calls for contrast, a bigger interval might be the way to go. If you’re aiming for something more nuanced, go smaller. But keep these things in mind:

  • There is such a thing as too much nuance: if a size on your scale is virtually indistinguishable from the sizes adjacent to it, it defeats the purpose of using a scale.
  • On the flip side, too much contrast renders the sizes’ proportional relationship moot. At a certain point, massive display type is arguably more graphic than textual.
  • More is less. The more sizes you use, the less they’ll mean.
A small interval (left, 1.1) offers a smoother range of sizes; a large interval (right, 1.8) offers more contrast.

Setting up the scale variables

The quickest way to get a scale up and running when working on the web is to drop its values into some CSS variables. The naming convention I typically use begins with --scale0, which is the body text size. The size below it is --scale-1 (as in “scale minus one”), the size above it is --scale1, and so on. Keeping the names relative to each other like this helps me move around the scale intuitively as I use it. If, say, --scale4 isn’t big enough for my h1, I can move up to --scale5 or --scale6, and I always know exactly how many steps away from the body text I am. Here’s a first pass at a simple set of scale variables using an interval of 1.5:

:root {
  --scale-2: 7.1px;  /* 10.7 ÷ 1.5 */
  --scale-1: 10.7px; /* 16 ÷ 1.5   */
  --scale0: 16px;    /* body text  */
  --scale1: 24px;    /* 16 × 1.5   */
  --scale2: 36px;    /* 24 × 1.5   */
}

I can use these variables with any CSS property that accepts a numeric value, like so:

p { font-size: var(--scale0); }

Rooting around in rems

I’m off to a good start. However, those px values are a little too absolute for my liking. If I convert them to rems, it’ll give my scale more flexibility. rem stands for “root em.” 1rem is equivalent to the html element’s text size, which in most browsers defaults to 16px. Crucially, though, users can adjust that size in their browser settings, and using rems in my CSS will respect those preferences.

:root {
  --scale-2: 0.4rem;  /* 0.7rem ÷ 1.5 */
  --scale-1: 0.7rem;  /* 1rem ÷ 1.5   */
  --scale0: 1rem;     /* body text    */
  --scale1: 1.5rem;   /* 1rem × 1.5   */
  --scale2: 2.25rem;  /* 1.5rem × 1.5 */
}

Another benefit of the relative nature of rems: I tend to use larger text sizes on large viewports and smaller text sizes on small viewports. Rather than adjusting dozens or hundreds of typographic CSS declarations per breakpoint, I can shift the whole scale up or down merely by adjusting the font-size on the html element:

html { font-size: 100%; }     /* 1rem = 16px */

@media screen and (min-width: 25em) {
  html { font-size: 112.5%; } /* 1rem = 18px */
}

Calculating with calc()

My scale is coming along. Its variables’ intuitive names make it easy for me to use, and its rem values respect the user’s browser preferences and allow me to easily shift the size of the entire scale at different viewport sizes. But my setup still isn’t optimized for one very important adjustment: the interval, which is currently 1.5. If 1.5 isn’t quite working for me and I want to see how an increase or decrease will affect the scale, I need to do the math all over again for every step in the scale every time I adjust the interval. The bigger the scale, the more time that will take. It’s time to put down the abacus and get calc() involved.

:root {
  --int: 1.5;
  --scale0: 1rem;
  --scale-1: calc(var(--scale0) / var(--int));
  --scale-2: calc(var(--scale-1) / var(--int));
  --scale1: calc(var(--scale0) * var(--int));
  --scale2: calc(var(--scale1) * var(--int));
}

My interval now has its very own variable, called --int. calc() determines each scale size by multiplying the preceding size by --int. Now that every size is ultimately dependent on --scale0’s value, --scale0 must appear first in the list. Since the sizes smaller than --scale0 are going down rather than up, their values require division rather than multiplication.

Scaling the scale

I can now quickly and easily tweak my scale’s interval by adjusting --int until the proportions are just right, but if I want to add more sizes to the scale, I need to add more variables and calc() values. This isn’t too big of a deal, but if I want to double or triple the number of sizes, it’s kind of a headache. Luckily, this is the sort of thing Sass is really good at. In the following code, adjusting the first four Sass variables at the top of :root will quickly spin up a set of CSS variables like the scale above, with any interval (proportional or fixed) and any number of scale sizes:

:root {
  $interval: 1.5;    // Unitless for proportional, unit for fixed
  $body-text: 1rem;  // Must have a unit
  $scale-min: -2;    // Unitless negative integer
  $scale-max: 2;     // Unitless positive integer

  --int: #{$interval};
  --scale0: #{$body-text};

  @if $scale-min < 0 {
  // Generate scale variables smaller than the base text size
    @for $i from -1 through $scale-min {
      @if type-of($interval) == number {
        @if unitless($interval) {
          --scale#{$i}: calc(var(--scale#{$i + 1}) / var(--int));
        } @else {
          --scale#{$i}: calc(var(--scale#{$i + 1}) - var(--int));
        }
      }
    }
  }
  @if $scale-max > 0 {
    // Generate scale variables larger than the base text size
    @for $i from 1 through $scale-max {
      @if type-of($interval) == number {
        @if unitless($interval) {
          --scale#{$i}: calc(var(--scale#{$i - 1}) * var(--int));
        } @else {
          --scale#{$i}: calc(var(--scale#{$i - 1}) + var(--int));
        }
      }
    }
  }
}

Go forth and scale

Typographic scales have been an indispensable part of my work for many years, and CSS variables and calc() make setup, adjustments, and experimentation easier than ever. I hope you find these techniques as useful as I do!


About the author

Rob Weychert is a Brooklyn-based designer. He helps shape the reading experience at ProPublica and has previously helped make books at A Book Apart, games at Harmonix, and websites at Happy Cog. In his free time, he obsesses over music and film. Despite all this, he is probably best known as a competitive air guitarist.

More articles by Rob




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With a 10,000-branch network, MD & CEO Goel eyes significant growth opportunities to expand business and scale new heights.



  • Money &amp; Banking

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DOI: 10.1039/D4QO01505C, Research Article
Open Access
Carlota Girón-Elola, Arkaitz Correa
A Pd-catalyzed directed C–H acylation of a collection of intricate phenol-containing compounds with ethanol and other alcohols and aldehydes is reported.
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Visible-light heterogeneous photocatalysis with an ionic porous organic polymer (IPOP): synthesis of β-keto sulfoxides and benzothiophene diesters by tandem radical addition–oxidation reactions

Org. Chem. Front., 2024, Advance Article
DOI: 10.1039/D4QO01382D, Research Article
Ajay Kumar Sahoo, Parag Tamuly, Jarugu Narasimha Moorthy
An IPOP, constructed constructed from cyanuric chloride and the readily accessible 2,5-di(pyridin-4-yl)thiazolo[5,4-d]thiazole (BpyTzTz), is shown to exhibit excellent visible light absorption and serve as a metal-free heterogeneous photocatalyst.
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Iron-catalyzed thiolation of C(sp3)–H with sulfonyl chlorides via photoinduced ligand-to-metal charge transfer

Org. Chem. Front., 2024, Advance Article
DOI: 10.1039/D4QO01488J, Research Article
Sheng-Ping Liu, Lan Yang, Yan-Hong He, Zhi Guan
A photoinduced FeCl3/HCl synergistic catalytic method enables C(sp3)–S bond formation via reductive cross-coupling of activated/inert C(sp3)–H and aryl/alkyl sulfonyl chlorides through ligand-to-metal charge transfer (LMCT).
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HSAB theory guiding electrophilic substitution reactions of o-carborane

Org. Chem. Front., 2024, Advance Article
DOI: 10.1039/D4QO01546K, Research Article
Yan Wang, Yi-Ge Li, Feijing Chen, Yan-Na Ma, Xuenian Chen
Herein, we systematically compared the reactivity of o-carborane and benzene toward different electrophiles and explained the results with the HSAB principle.
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Photocatalytic arylation/alkylation of olefins/alkynes via halogen-atom transfer mediated by NHC-BH3

Org. Chem. Front., 2024, Advance Article
DOI: 10.1039/D4QO01562B, Research Article
Xinhan Li, Yao Zhong, Fengsong Tan, Yusong Fei, Xiaohan Zhao, Jianbin Xu, Baomin Fan
A versatile method for radical reductive cross-coupling of iodides and activated olefins under mild conditions, facilitated by NHC-BH3 through photocatalysis, was developed.
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Photoinduced cobaloxime catalysis for allylic mono- and diphosphinylation of alkenes with hydrogen evolution

Org. Chem. Front., 2024, Advance Article
DOI: 10.1039/D4QO01638F, Research Article
Aijun Zhang, Miao-Miao Li, Lei Guo, Huaixiang Yang, Jiefei Guo, Da Xu, Wei Ding
A highly efficient allylic radical mono- and diphosphinylation of alkenes with secondary phosphine oxides is developed, via visible-light-induced cobaloxime catalysis.
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Visible-light mediated selective phosphonylation modification of tryptophan residues in oligopeptides

Org. Chem. Front., 2024, 11,6287-6292
DOI: 10.1039/D4QO01028K, Research Article
Wenfang Xiong, Junye He, Jinyao Liu, Peiru Chen, Shiqi Xu, Yipeng Liu, Shiting Chen, Yuanyuan You, Zhenyu Chen, Jinwu Zhao
A direct C2-H phosphonylation strategy driven by visible light for specific modification of tryptophan-containing peptides has been reported, providing a plethora of phosphorylated tryptophan-containing peptides
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Iridium/palladium dual photocatalysis for oxidative decarboxylative esterification of alcohols using α-keto acids

Org. Chem. Front., 2024, 11,6367-6379
DOI: 10.1039/D4QO01452A, Research Article
Subal Mondal, Soumya Mondal, Debabrata Halder, Siba P. Midya, Ankan Paul, Pradyut Ghosh
Herein, we report an unprecedented oxidative decarboxylative C–O cross-coupling reaction for the esterification of feedstock α-keto carboxylic acids and alcohols under mild conditions.
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Structure determination of difficult-to-crystallize organic molecules by co-crystallization of a phosphorylated macrocycle

Org. Chem. Front., 2024, 11,6358-6366
DOI: 10.1039/D4QO01498G, Research Article
Heng Li, Zhijin Li, Juli Jiang, Chen Lin, Leyong Wang
This work reported that 37 different difficult-to-crystallize guest molecules were co-crystallized with the host macrocycle F[3]A1-[P(O)Ph]3 at room temperature, and the molecular structures of the guests could be determined by SCXRD.
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Phosphine-controlled divergent reactions of MBH-carbonates with azaheptafulvenes: access to o-anilinyl diene and benzazepine derivatives

Org. Chem. Front., 2024, 11,6418-6425
DOI: 10.1039/D4QO01298D, Research Article
Wei Hao, Yiwen Zhang, Xiao Han, Zhen Wang, Weijun Yao
A phosphine controlled divergent cascade reaction of MBH-carbonates with azaheptafulvenes was disclosed. PPh3 provided o-aminophenyl diene while PCy3 offered benzazepine derivative through formal [8 + 3] annulation/ring contraction cascade.
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A cucurbit[8]uril-mediated host–guest complex for red-light photocatalysis

Org. Chem. Front., 2024, 11,6327-6332
DOI: 10.1039/D4QO01492H, Research Article
Weiquan Xu, Yinghao Du, He Ma, Xingchen Tang, Jiang-Fei Xu, Xi Zhang
Two-step host–guest complexation can occur between an elongated dye and CB[8], leading to the formation of CB[8]@2TPP and 3CB[8]@2TPP sequentially. Of these species, 3CB[8]@2TPP in particular can act as an efficient red-light photocatalyst.
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Chiral synthetic unprecedented spiro[indoline-2,3'-thiophen]-3-ones via an organocatalytic asymmetric sulfa-Michael/aldol cascade reaction

Org. Chem. Front., 2024, 11,6426-6436
DOI: 10.1039/D4QO01551G, Research Article
Mao Zhang, Xing-Hai Fei, Gui-Ping Yang, Cheng Lin, Wen-Jie Li, Ming-Liang Rao, Meng Zhou, Chong Zhao, Bin He, Yong-Long Zhao
A cinchona-derived squaramide-catalyzed asymmetric sulfa-Michael/aldol cascade reaction of 2-ylideneoxindoles with 1,4-dithiane-2,5-diol was developed to realize the chiral synthesis of spiro[indoline-2,3'-thiophen]-3-ones.
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Visible light-induced aerobic photooxidative cleavage of C(sp3)–C(sp2) σ-bonds of allylarenes

Org. Chem. Front., 2024, 11,6385-6392
DOI: 10.1039/D4QO01243G, Research Article
Jinyu Tang, Xi Zhao, Jinxuan Ni, Yanping Huo, Yang Gao, Xianwei Li, Yan Liu, Keiji Maruoka, Qian Chen
A cleavage of C(sp3)–C(sp2) σ-bonds of allylarenes to aromatic aldehydes and ketones has been achieved via a visible light-induced photocatalysis.
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Theoretical insights into Pd-catalyzed dual γ-1,1-C(sp3)–H activation of aliphatic carboxylic acids: mechanistic pathways, substituent influence on product selectivity, diastereoselectivity, and additive effects

Org. Chem. Front., 2024, 11,6393-6410
DOI: 10.1039/D4QO01451K, Research Article
Jiaoyang Liu, Li-juan Huang, Zeang Sun, Juan Li
DFT calculations were employed to explore the detailed reaction mechanism and the origins of the experimentally observed product, regio-, and diastereoselectivities in the Pd-catalyzed dual-γ-1,1-C(sp3)–H activation of aliphatic carboxylic acids.
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Nickel-catalysed enantioselective cross-electrophile coupling reaction with the retention of the β-fluorine atom

Org. Chem. Front., 2024, 11,6459-6469
DOI: 10.1039/D4QO01555J, Research Article
Xin-Yi Shi, Xueyuan Yan, Xiaodong Tang, Shi-Jing Zhai, Genping Huang, Jun-An Ma, Fa-Guang Zhang
A nickel-catalysed enantioselective reductive cross-coupling reaction of a new monofluoromethyl building block with acid chlorides is developed to give chiral α-monofluoromethyl acyloin derivatives.
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Activation of donor–acceptor cyclopropanes under basic conditions: ring opening of 2-(p-siloxyaryl)cyclopropane 1,1-dicarboxylates with nitro compounds and other C-nucleophiles

Org. Chem. Front., 2024, 11,6483-6494
DOI: 10.1039/D4QO01472C, Research Article
Yulia A. Antonova, Andrey A. Tabolin
A new activation mode for donor–acceptor cyclopropanes was proposed and implemented in their reaction with nitro compounds and other common C-nucleophiles.
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Carbonate-assisted selectively deoxygenative cross-coupling reaction between aryl and aliphatic aldehydes: a straightforward route to access α-alkylated aryl ketones

Org. Chem. Front., 2024, 11,6510-6517
DOI: 10.1039/D4QO01517G, Research Article
Yu Sun, Yi Wang, Zhijun Zuo
A novel reductive cross-coupling reaction of two different aldehydes for rapidly assembling α-alkylated aryl ketones has been developed. The inexpensive carbonate served not only as a base but also as an efficient electron donor.
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Anomalous magnetic behaviour induced by a structural phase transition with anisotropic thermal expansion in a spirodiradical

Org. Chem. Front., 2024, 11,6495-6502
DOI: 10.1039/D4QO01098A, Research Article
Open Access
Takuya Kanetomo, Daigo Matsunaga, Shinichi Ogawa, Masaya Enomoto
A Ge-centred spirodiradical exhibited anomalous magnetic behaviour, influenced by two key structural factors: negative thermal expansion and a structural phase transition.
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Sulfenylation of bioactive maleimides, acrylates and cyclohexenones under ambient organophotocatalysis

Org. Chem. Front., 2024, 11,6503-6509
DOI: 10.1039/D4QO01342E, Research Article
Debanjana Bag, Rajjakfur Rahaman, Anindya S. Manna, Subhasis Pal, Rajesh Nandi, Shobhon Aich, Narendra Nath Ghosh, Dilip K. Maiti
A novel visible light-induced sulfenylation of biologically important maleimides, acrylates and cyclohexenones has been developed using cheap and easily available organophotoredox catalyst Eosin Y with thiols under ambient conditions.
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Shining light on sulfonium salts and sulfur ylides: recent advances in alkylation under photoredox catalysis

Org. Chem. Front., 2024, 11,6573-6588
DOI: 10.1039/D4QO01644K, Review Article
Zhe Jin, Tingwei Yu, Hui Wang, Penghao Jia, You Huang
Recent advancements in photoredox alkylation with sulfur ylides, sulfonium salts and related analogues are summarized in this review.
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Dendron-mediated control over self-assembly of chlorophyll rosettes into columnar vs. discrete aggregates

Org. Chem. Front., 2024, 11,6304-6310
DOI: 10.1039/D4QO01629G, Research Article
Open Access
  This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
Ryo Kudo, Hiroki Hanayama, Balaraman Vedhanarayanan, Hitoshi Tamiaki, Nobuyuki Hara, Sarah E. Rogers, Martin J. Hollamby, Biplab Manna, Koji Harano, Shiki Yagai
By controlling the π-π stacking of chlorophyll supramolecular rosettes through steric hindrance of alkyl dendrons, it become possible to create chlorophyll tubes and discrete rings that resemble to natural chlorophyll assemblies.
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