There are several problems in what you are trying to do.
The obvious one is that splines abhor singularities, and you have one on the left end of that curve. Made up of polynomial segments, you can expect them to fail there.
As well, a standard least squares spline, or a smoothing spline both assume the error is in y only. But you clearly have a cloud that spreads out along the curve in both directions. So any least squares or smoothing spline must perform poorly. So I would not even bother trying to use my own SLM toolbox on this data.
Orthogonal regressions using splines are difficult.
I see that you have supplied the data, so I'll take a look at it. Perhaps I can make a stab at something...
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